Complex chromium compounds of ortho-hydroxyazo dyestuffs and their production



Patented Mar. 10, 1936 UNITED STATES PATENT OFFICE COMPLEX CHROlVIIUMCOMPOUNDS OF' ORTHO-HYDROXYAZO DYESTUFFS AND THEIR PRODUCTION NoDrawing.

Application May 27, 1933, Serial No. 673,306. In Germany June 4, 1932 9Claims. (01. 260-12) The present application relates to new complexchromium compounds of ortho-hydroxyazo dyestufis and a process ofproducing same.

We have found that valuable complex chromium compounds ofortho-hydroxyazo dyestuffs are obtained by coupling the diazoniumderivatives of compounds corresponding to the follow ing formula whereinX stands for a benzene or naphthalene radicle, A for an alkyl or acylgroup and each Z for hydrogen or an alkyl, cycloalkyl, aralkyl or arylradicle and wherein the oA-group and the NHz-group are fixed to X inortho-position to one another, with coupling components containing atleast one sulphonic group, the resulting dyestuffs being treated withagents supplying chromium under conditions under which splitting off 5of the radicle A takes place. In this manner dyestuffs of good levellingpower and which on animal fibres such as wool, silk and leather yielddyeings especially fast to light and washing are obtained. The dyestuffsmay be used for dyeing as well as for printing. Sulphamides ofortho-aminophenol or ortho-aminonaphthol ethers or esters the" diazocompounds of which are to be used may contain further substituents suchas further alkoxy groups, halogen, alkyl or nitro groups. The phenolichydroxyl groups may be etherified with aliphatic alcohols to form methylor ethyl ethers or they may be esterified with carboxylic or sulphonicacids. As the radicle A is split 01f from the phenolic hydroxyl groupduring the reaction, it is, of course, preferable to use initialmaterials as are available most readily; for. this reason. in most,casesthe methyl ethers of the compounds in question are used; ethylethers and the like may, however, be used with asimilar effect; It isadvantageous to carry out the treatment of dyestuifs derived from.

ethers of the kind defined above in acid media. If dyestufis derivedfrom esters, such as toluenesulphonic acid esters, are used thetreatment with agents supplying chromium is'pr'eferably effected inmedia having an alkaline reaction.

One or both hydrogen atoms of the sulphamido radicle contained the diazocompound, 5 which may occupy any position in relation to the diazogroup, may be substituted by alkyl, cycloalkyl, aralkyl or arylradicles.

The coupling components containing at least one sulphonic group may beof any kind. Naphtholsulphonic acids give very satisfactory results. 5According to the different components dyestuffs yielding differentshades, for example yellow, Bordeaux or blue shades, can be obtained.

The conversion of the azo dyestuffs into the complex chromium compoundsis carried out by 10 known methods under such conditions that asplitting off of alkyl or acyl radicles from the hydroxyalkyl orhydroxyacyl groups takes place.

The treatment is effected by heating the azo dyestuffs with agentssupplying chromium in the 16 presence of water at temperatures betweenabout and 150 C. When the reaction is carried out at higher temperaturesbeing within this range the reaction proceeds more readily; thereforethe use of temperatures above 100 C. and 20 working under pressure isadvantageous. The process may be carried out for example as indicated inPatent No. 1,765,680. Suitable agents supplying chromium are for exampleaqueous solutions of chromium fluoride, chromium for- 25 mate, chromiumsulphate, chromium alum or alkaline chromite solutions.

The ortho-hydroxyazo dyestufis may be first prepared from the dyestuffs,the former being treated with agents supplying chromium. so

The following examples will further illustrate the nature of thisinvention, but the invention is not restricted to these examples. Theparts are by weight.

Example 1 35 258 parts of Z-amino-1-anisol-4-sulphodiethylamide(obtainable by converting 2-nitro-1-anisol-i-sulphonic acid into thesulphonic acid 40 chloride, preparing from the latter the correspondingsulphodiethylamide by treatment with diethylamine and reducing the nitrogroup) are diazotized in the usual manner and coupled with a solution.rendered alkaline with sodium car- 4 bonate, of 330 parts of2+naphthol-6,8-disulphonic acid. The dyestuff, separated by the additionof common salt, dyes wool level very brilliant orange shades havinghigh, fastness to light.

In order to prepare the complex chromium compound from the azo dyestufi,the latter is heated in an autoclave for about .3 hours at C. with anaqueous solution of chromium sulphate or chromium formate containing 60parts of chromium, preferably while stirring. When the chroming iscompleted, the dyestuff solution is evaporated to dryness; the dyestufimay also be deposited from its solution by the addition of hydrochloricor sulphuric acid. The dyestufi thus obtained dyes wool beautiful bluishBordeaux red shades. In addition to great levelness, the dyeing isdistinguished by very good fastness to light and washing; the dyestufidoes not dye cotton or viscose artificial silk.

Example 2 Shades of color similar to those obtained with the dyestuifdescribed in Example 1 are obtained by employing instead of the diazocomponent described in Example 1 the 2-amino-l-anisol- 4-sulphamides inwhich the amido group is sub-'- stituted by one ethyl or by one or twomethyl groups or by two phenyl groups and working otherwise in the samemanner as set forth in the said example.(Z-amino-l-anisol-4-sulphodiphenylamide can be obtained by converting 2-nitro-l-anisoll-sulphonic acid into the chloride, preparing from thelatter the corresponding dip-henylamide by treatment with diphenylamineand reducing the nitro group. When using the compound thus formed adyestufi is obtained which dyes silk very well.) 5-chlor-2-amino-l-anisol 4-sulphamide (obtainable by acetylating5-chlor-2-amino-l-anisol, converting the acetylation product obtainedinto the sulphochloride by means of chloro sulphonic acid, preparingtherefrom the corresponding amide by means of aqueous ammonia andsaponifying the acetyl amino sulphamide) may be used as diazo componentwith a similar efiect. Similar shades of color are also obtained byemploying 2-naphthol-8-sulphonic acid as the coupling component incombination with the diazo compounds described in the preceding exampleand in this paragraph of the present example.

The dyestuffs listed in the following table, for example, may also beprepared in a corresponding manner. One method suitable for preparingdiazo components of the type to be used according to the presentinvention consists in starting with the corresponding sulphonic acidscontaining a nit'ro group instead of the amino preparing therefromsulphochlorides, converting the latter into sulphamides by treatmentwith ammonia or the appropriate amine and reducing the nitrosulphamidesto form the aminated sulphamides. The diazo components may be preparedalso according to other methods as indicated in the first column of thetable.

Shade of chromium compound Dyestufl from Shade Yellow Orange.

Yellow Red.

Yellow brown; Rose red.

Shade tainable by melting Nsacetyl-5- sulpho-anthranillc acid withcaustic alkali at above 200 0., N ecetyl 5 sulphoanthranilic acid may beprepared by sulphonating anthranilic acid at between and C. by means of23 per cent fuming sulphuric acid and acetylating the 2-amino-5-s'ulpho-benzoic acid by means of acetic acid anhydride in theusual manner).

Diazotized 6-methoxy-2-amino-1- anisoli-sulphamide (obtainable byacetylating 2-amino-l,5- resorcm dimethyl ether, treating withchlorosulphonic acid, converting the sulphochlorlde obtained by means ofaqueous ammonia into the acetyl aminosulphamide and saponilying thelatter with dilute caustic soda solution) and 2,3,6-naphtholdisulphonicacid.

Diazotized 4-chlor-2-amino l-anisol-5-sulpho-diethylamide (prepared asdescribed in Example 2 of the table while using diethylamine instead 01'ammonia) and 2,6,8-naphthol disulphonic acid.

Diazotized 4-chlor-2-amino-1-anisol-fi-sulpho-diethylamide (see thepreceding example) and 2,3,6-na'phthol disulphonic acid.

Diazotized 2-atninohydr0quinone dimethyl ether 5 sulphamide (obtainableby acetylating 2- amino-1,4-hydroquinone dimethyl ether, treating theacetyl product with chlorosulphonic acid, converting the sulphochlorideobtained with aqueous ammonia into the acetylaminosul hamide andsaponifying t e latter by means of dilute caustic soda solution) and2,6,8- naphthol disulphonic acid.

Diazotized Z-aminohydroquinone dimethylether- 5 -sulph'odiethylamide(obtainable in a cone spending manner as described in the precedingexample while using diethyl amine instead of ammonia) and 2,3,6-naphtholdisulphonic acid.

Diazotized 4'ch1or-2-amino-l-anisolfi-sulphamide (see Example 2 of thistable) and 2,4-naphthol sulphonic acid.

Diazotized 5-methoxy-2-amino-1- anisol-4-sulphamide (see Example 4 01'this table) and 2,8- dihydroxynaphthalene 6 sul phonic acid.

Diazotized Z-amino-l-anisol-4-sulphodiethylamide andS-hydroxyquinoline-E-sulphonic acid.

Diazotized l-amino-2-naphtholmethylether 6 sulphodiethyl amide and1,4,8-naphtholdisulphonic acid.

Diazotized l-amino-2-naphtholmethyiether 6 sulphodiethyl amide andl-naphth'bl-S-sulphemide-3 sulphonic acid.

Diazotized l-amino-2-naphtholmethylether 6 sulphodiethyl amide andl-naphthoM-sulphodiethylamide-S-sulphonic acid (obtainable by convertinglnaphthol--sulphonic acid or its toluene sulphonic acid ester into thesulphonic acid amide by way of the sulphochloride and 'sulphonating thesulphamide obtained).

Bordeaux red- Bright 'red- Red Bordeaux red Crimson red Bordeaux red-Bordeaux red.

Red

Violet red Red violet.

Violet Red violet.

Violet.

Blue violet.

Blue.

Blue.

Blue.

Blue green.

Yellow brown.

Blue.

Green blue.

Green blue.

What we claim is:

1. Complex chromium compounds of orthohydroxyazo dyestufis correspondingto the general formula:

I Og-N wherein X stands for a benzene or naphthalene radicle, Y for theradicle of a coupling compound selected from the group consisting ofhydroxynaphthalenes, hydroxyquinolines, and pyrazolones, Z1 stands foralkyl, Z2 for hydrogen or alkyl, n for a whole number and wherein the OHand the -N=M groups are fixed to X in ortho-position to one another.

2. Complex chromium compounds of orthohydroxyazo dyestuffs correspondingto the general formula:

wherein X stands for a benzene or naphthalene radicle, Y for the radicleof a coupling compound selected from the group consisting ofhydroxynaphthalenes, hydroxyquinolines, and pyrazolones, Z1 stands foralkyl, Z2 for hydrogen or alkyl, n for a whole number from 1 to 2 andwherein the OH and the -N=N-- groups are fixed to X in ortho-position toone another.

3. Complex chromium compounds of the orthohydroxyazo dyestuffscorresponding to the general formula i SOr-N eral formula SOr-N SOzHwherein Z1 stands for alkyl and Z2 for hydrogen or alkyl.

5. The complex chromium compound of the ortho-hydroxyazo dyestuficorresponding to the formula 6. The complex chromium compound of thepressure.

ortho-hydroxyazo dyestufi corresponding to the formula (I)H HO HOaS CHSOz-N 0111 8. The process of producing complex chromium compounds ofortho-hydroxyazo dyestuffs which comprises heating a compoundcorresponding to the general formula wherein A stands for an alkyl oracyl radicle, X for a benzene or naphthalene radicle, Y for the radicleof a coupling compound selected from the group consisting ofhydroxynaphth-alenes, hydroxyquinolines, and pyrazolones, Z1 stands foralkyl, Z2 for hydrogen or alkyl, n for a whole number and wherein the OAand the --N=N groups are fixed to X in ortho-position to one another, inthe presence of water at temperatures between about 100 and 150 C. withan agent supplying chromium.

9. The process of producing complex chromium compounds ofortho-hydroxyazo dyestuifs which comprises heating a compoundcorresponding to the general formula wherein A stands for an alkyl oracyl radicle, X for a benzene or naphthalene radicle, Y for the radicleof a coupling compound selected from the group consisting ofhydroxynaphthalenes, hydroxyquinolines, and pyrazolones, Z1 stands foralkyl, Z2 for hydrogen or alkyl, n for a whole number and wherein the OAand the -N=N- groups are fixed to X in ortho-position to one another, inthe presence of water at temperatures between about 100 and 150 C. withan agent supplying chromium under elevated HANS KRZIKALLA. WALTHERKUEHNE.

